EP0423624B1 - Color-coated article and method for producing the same - Google Patents

Color-coated article and method for producing the same Download PDF

Info

Publication number
EP0423624B1
EP0423624B1 EP90119534A EP90119534A EP0423624B1 EP 0423624 B1 EP0423624 B1 EP 0423624B1 EP 90119534 A EP90119534 A EP 90119534A EP 90119534 A EP90119534 A EP 90119534A EP 0423624 B1 EP0423624 B1 EP 0423624B1
Authority
EP
European Patent Office
Prior art keywords
phase
layer
zinc hot
dip galvanizing
weight
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP90119534A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0423624A1 (en
Inventor
Hiroshi Tasaki
Yasunori Yamamoto
Eiji Nishimura
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nippon Mining Holdings Inc
Original Assignee
Nippon Mining and Metals Co Ltd
Nippon Mining Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP1105819A external-priority patent/JPH07110962B2/ja
Priority claimed from JP2125486A external-priority patent/JPH0765149B2/ja
Priority claimed from JP2131207A external-priority patent/JP2612954B2/ja
Application filed by Nippon Mining and Metals Co Ltd, Nippon Mining Co Ltd filed Critical Nippon Mining and Metals Co Ltd
Publication of EP0423624A1 publication Critical patent/EP0423624A1/en
Application granted granted Critical
Publication of EP0423624B1 publication Critical patent/EP0423624B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/48—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
    • C23C22/53—Treatment of zinc or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
    • C23C2/06—Zinc or cadmium or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/26—After-treatment
    • C23C2/28—Thermal after-treatment, e.g. treatment in oil bath
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/24—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing hexavalent chromium compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/32—Spheres
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/32—Thermal properties
    • C01P2006/33—Phase transition temperatures
    • C01P2006/34—Melting temperatures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional purity

Definitions

  • the present invention relates to a color coated-article and method for producing the same. More particularly, the present invention relates to a color coated-article, in which the zinc hot-dip galvanizing layer is developed to produce the color brown, as well as to a method for producing the same.
  • color can be developed using the method of color interference.
  • zinc hot-dip galvanizing is carried out in a plating bath with additives of approximately 0.5% by weight of Mn and/or Ti, and, then, the plating layer is oxidized to form an oxide layer of Ti and/or Mn.
  • This method involves, however, a drawback in that the color is not maintained for a long period, and, further, the shades of brown are not formed because the color development is due to interference.
  • a brown appearance is sometimes desired, since it harmonizes with the surroundings and environment.
  • the color initially developed on, for example, a steel tower is stably maintained, an observer does not have the impression that the color has faded. Since a spotted appearance is not given, the stability of color is desirable from the point of view of aesthetics.
  • a brown coated article which consists of an iron substrate, a zinc hot-dip galvanizing layer consisting essentially of from 1 to 15% by weight of Fe and from 0.05 to 1% by weight of Mn, and the balance of Zn, and a brown Zn-Mn-Fe oxide layer which is present on the top surface of the zinc hot-dip galvanizing layer, a zeta phase being present on said top surface beneath said oxide layer.
  • the desired brown color is developed by means of oxidizing the surface of the zinc bot-dip galvanizing layer containing the above mentioned content of Fe and Mn.
  • the brown color herein is the one indicated by 5Y/L - Dk, 5YR/Dk and 5Gy/Dk of Hue and Tone Graph ("Color Image Dictionary” published by Kodansha on May 20, 1989, page 186).
  • This brown color is not developed by the conventional, zinc hot-dip galvanizing layer exhibiting the interference color, but is the color of the Zn-Mn-Fe oxide per se.
  • the above mentioned content of Fe and Mn is desirable for weather resistance, since the brown color does not fade easily when the coating article is exposed to weather.
  • the zinc hot-dip galvanized article to be subjected to the preparation of the brown coated article, hereinafter referred to as the intermediate article, according to the present invention is characterized in that:
  • the zinc hot-dip galvanizing layer of the intermediate articles preferably contains from 1 to 15% by weight of Fe and from 0.05 to 1% by weight of Mn.
  • Zinc used for the plating bath in the method according to the present invention may be distilled zinc metal, grade 1 (98.5% or more of purity), the purest zinc metal (99.995% by weight or more of purity), or electric zinc metal (99.99% by weight or more of purity).
  • the distilled zinc metal, grade 1, mentioned above contains 1.5% by weight or less of Pb, 0.1% by weight or less of Cd, and 0.02% by weight or less or Fe as the impurities.
  • Pb and/or Cd zinc metal containing 0.005% by weight or less of these elements should be used.
  • the purest zinc metal or electric zinc having 0.01% by weight or less of the total contents of the impurities should be used.
  • the plating is carried out using the bath of molten zinc with the additive of from 0.05 to 1.0% by weight of Mn.
  • the Mn in an amount of from 0.05 to 1.0% by weight is necessary for developing the brown color in the succeeding oxidizing treatment. It is not necessary to add Fe to the molten zinc bath, because Fe is fed to the zinc hot-dip galvanizing layer from the steel substrate. A part of from 1 to 15% by weight of Fe may however be present in the molten zinc bath.
  • an iron object is dipped in the above mentioned plating bath at a temperature of from 430 to 480°C, for at least 1 minute.
  • a Mn-oxide phase is present on the surface of this plated iron substrate.
  • a Zn-Mn phase is present on the surface of this plated iron substrate.
  • a Zn-Mn-Fe phase is present and extends to the steel substrate.
  • the Mn-oxide phase and the Zn-Mn phase are removed mechanically, e.g., by grinding, or chemically, e.g., by etching, so as to expose the Zn-Mn-Fe phase, which is then oxidized.
  • the Zn-Mn phase is totally converted to the Zn-Mn-Fe phase by means of heating after the plating.
  • the Zn-Mn-Fe phase is then oxidized.
  • Heating is desirably carried out at a temperature of from 440 to 600°C for from 30 seconds to less than 100 minutes. This heating only leads to the development of greenish brown.
  • the coated article in which the top layer is the Mn-oxide phase and the underlying layer is the Zn-Mn-Fe phase by the moisture in the air and by rain, and then the surface of the Zn-Mn-Fe phase is oxidized, thereby developing a brown color after one or two months.
  • the treatment by this method takes too long.
  • the plated and then heated pieces are dipped in an acidic solution containing an oxidizing agent.
  • the Mn-oxide phase is dissolved and the surface of the Zn-Mn-Fe alloy phase is oxidized.
  • the oxidizing agent herein may by any capable of oxidizing the Zn-Mn-Fe alloy.
  • H2O2, O2, KMnO4, K2Cr2O7, and NaNO2 are preferred as the oxidizing agent, especially KMnO4 and K2Cr2O7.
  • the acid may be any capable of dissolving the Mn oxide. Mineral acid is preferred, of which H2SO4, HCl, and HNO3 are especially preferred.
  • pH of the acidic solution may be such that the Mn-oxide is dissolved, but the Zn-Mn-Fe alloy is not dissolved drastically, and, further, the oxidation effect of the oxidizing agent is not impeded essentially.
  • the pH level is preferably from 1 to 3. Below pH 1, the Zn-Mn-Fe alloy is considerably dissolved. Above pH 3, a long time is required for the color development.
  • a brown color is developed by means of immersing the object under preferred conditions, for from several tens of seconds to several minutes.
  • the zinc hot-dip galvanizing layer formed by using the Mn-containing plating bath may peel from the iron substrate during cooling after the zinc hot-dip galvanizing, or may crack during the post-plating heating step.
  • This problem is associated with the fact that, when the zinc hot-dip galvanizing layer contains Mn, Mn promotes the alloying of Fe and Zn and hence facilitates formation of ⁇ 1 phase (FeZn7 phase) in the zinc hot-dip galvanizing layer. It turned out that the ⁇ 1 phase present in the top surface of the zinc hot-dip galvanizing layer makes the peeling and cracking of the plating layer easy to take place.
  • the multi-layer structure of the intermediate article (1) mentioned above is preferred, i.e., the top layer of the zinc hot-dip galvanizing layer is ⁇ phase, and its underlaying layer is ⁇ phase.
  • the ⁇ phase has the hexagonal structure of pure zinc, and contains in this structure 0.05 - 1% by weight of Mn and 0.003% by weight of Fe as the solute atoms. The balance of Mn and Fe is Zn except for the unavoidable impurities.
  • phase is based on the FeZn12, in which the coloring elements, such as 0.05 - 1% by weight of Mn, are contained. These two phases contain less Fe than the ⁇ 1 phase.
  • these two phases have therefore features that: they are formed by the suppression of the reaction of Fe and Zn: further, they are highly resistant to the internal stress generated in the plating layer during the post-plating cooling, and to the external stress applied to the plating layer during the post-plating heating.
  • the temperature of the plating bath should be set in the preferred range mentioned above. When the temperature of the plating bath is lower than 430°C, the zinc hot-dip galvanizing becomes difficult. On the other hand, when the temperature of the plating bath is higher than 480°C, the ⁇ phase disappears, and the reaction between Fe and Zn is undesirably promoted by Mn under the effects of the high temperature, thereby resulting in active formation of the ⁇ 1 phase.
  • Fig. 1 is a microscope photograph (magnification 500) showing the cross sectional structure of a coating of a steel substrate, which has been zinc hot-dip galvanized in a plating bath as 480°C for 3 minutes, and then heated at 490°C for 6 minutes.
  • Fig. 2 is a microscope photograph (magnification 500) showing the cross sectional structure of a coating of a steel substrate, which has been zinc hot-dip galvanized in a plating bath at 540°C for 3 minutes, and then heated at 540°C for 10 minutes.
  • the zinc hot-dip galvanizing layer shown in Fig. 1 an ⁇ phase (top layer) and ⁇ phase (lower layer) were formed directly after the plating.
  • the ⁇ phase was decomposed, due to the heating at 490°C, into the top part mainly composed of the Mn oxide, and the underlying part which was changed to the ⁇ phase.
  • the intermediate article (2) according to the present invention was therefore provided.
  • the ⁇ phase formed by the zinc hot-dip galvanizing remains, but becomes thicker, due to heating, as compared with the thickness directly after the plating.
  • the thickness of the ⁇ 1 phase becomes greater somewhat due to the heating.
  • the thickness change is however not prominent.
  • the sample treated as described above did not crack.
  • the Mn-oxide layer of the sample teated as above was dissolved, followed by converting the ⁇ phase to an oxide. As a result, the desired brown color could be obtained.
  • a crack was generated during the heating at 540°C.
  • the reason for the crack generation was that the temperature of the plating bath, at 540°C, was too high.
  • the layer-structure after heating was such that Mn-oxide constituted the surface layer, and, further, the ⁇ 1 phase was present consistantly between the surface layer and the iron substrate.
  • This ⁇ 1 phase had a composition of Zn-Mn-Fe and developed a brown color by means of oxidizing.
  • a steel sheet (SS41) 50mm in width, 100mm in length, and 3.2mm in thickness was dipped for 30 minutes in an alkaline bath having a temperature of 80°C to degrease it.
  • the steel sheet was then rinsed with hot water, and was then dipped for 30 minutes in a 10% hydrochloric acid solution at room temperature to descale it.
  • the steel sheet was subjected to a hot water rinse and then a flux treatment using a 35% ZnCl2 - NH4Cl solution by dipping for 30 minutes in this solution at 60°C.
  • the steel sheet which was subjected to the pretreatment as described above, was dipped for 1 minute in a plating bath containing 0.5% by weight of Mn, the balance being Zn at 500°C. After the zinc hot-dip galvanizing the steel sheet was lifted above the plating bath and kept for 60 seconds in a furnace at 500°C so as to heat-treat the steel sheet. After the heat treatment, the steel sheet was allowed to cool, and then dipped for 1 minute in a sulfuric acid solution containing 4g/l of KMnO4 and having pH of 2.
  • a uniform brown color corresponding to 5Y/Dk of the Hue and Tone Dictionary was formed on the surface of the zinc hot-dip galvanizing layer.
  • the brown color developed was due to the oxide layer formed on the surface of the zinc hot-dip galvanizing layer.
  • the composition of the coating was 0.5% by weight of Mn, 7% by weight of Fe, and the balance being Zn, directly after the zinc hot-dip galvanizing.
  • a steel sheet (SS41) 50mm in width, 100mm in length, and 3.2mm in thickness was dipped for 30 minutes in an alkaline bath having a temperature of 80°C to degrease it.
  • the steel sheet was then rinsed with hot water and was then dipped for 30 minutes in a 10% hydrochloric acid solution at room temperature to descale it.
  • the steel sheet was subjected to a hot water rinse and then a flux treatment using a 35% ZnCl2 - NH4Cl solution by dipping for 30 minutes in this solution at 60°C.
  • the steel sheet which was subjected to the pretreatment as described above, was dipped for 1 minute in a plating bath containing 0.5% by weight of Mn, the balance being Zn at 500°C. After the zinc hot-dip galvanizing, the steel sheet was lifted above the plating bath and kept for 60 seconds in a furnace at 500°C so as to heat-treat the steel sheet. After the heat treatment, the steel sheet was allowed to cool, and then dipped for 1 minute in a sulfuric acid solution containing 4g/l of K2Cr2O7 and having pH of 2.
  • a uniform brown color corresponding to 5Y/Dk of the Hue and Tone Dictionary was formed on the surface of the zinc hot-dip galvanizing layer.
  • the brown color developed was due to the oxide layer formed on the surface of the zinc hot-dip galvanizing layer.
  • the composition of the coating directly after the zinc hot-dip galvanizing was 0.5% by weight of Mn, 7% by weight of Fe, and the balance being Zn.
  • a steel sheet pretreated as in Example 1 was dipped for 3 minutes in a Zn-alloy bath containing 0.3% by weight of Mn.
  • the temperature of the Zn-alloy plating bath was fixed at 460°C.
  • the steel sheet was allowed to cool so as to prepare the intermediate article.
  • the zinc hot-dip galvanizing layer of the intermediate article contained 5% by weight of Fe and 0.3% by weight of Mn.
  • the so-treated sample, i.e., the intermediate article (1) was subjected to examination for the presence (absence) of peeling and cracks as well as examination of the layer structure. It turned out that the top layer and its underlying layer were ⁇ phase and ⁇ phase, respectively. Neither peeling of the plating layer nor cracking of the plating layer was observed in the zinc hot-dip galvanizing layer after the cooling.
  • a steel sheet pretreated as in Example 1 was dipped for 3 minutes in a Zn-alloy bath containing 0.2% by weight of Mn.
  • the temperature of the Zn-alloy plating bath was fixed at 450°C.
  • the zinc hot-dip galvanizing the steel sheet was allowed to cool.
  • the steel sheet was heated at 500°C for 10 minutes and was allowed to cool.
  • the zinc hot-dip galvanizing layer of the intermediate article contained 9% by weight of Fe and 0.2% by weight of Mn.
  • the so-treated sample, i.,e., the intermediate article (2) was subjected to examination for the presence (absence) of peeling and cracks as well as examination of the layer structure.
  • the top layer of the zinc hot-dip galvanizing layer was greenish brown and was mainly composed of MnO, and, further, its underlying layer was composed of ⁇ phase. No peeling of the plating layer was observed. By using an optical microscope at a magnification of 200, no cracking of the plating layer was observed in the zinc hot-dip galvanizing layer.
  • a steel sheet pretreated as in Example 1 was dipped for 3 minutes in a Zn-alloy bath containing 0.3% by weight of Mn.
  • the temperature of the Zn-alloy plating bath was fixed at 500°C.
  • the zinc hot-dip galvanizing the steel sheet was allowed to cool so as to prepare the intermediate article.
  • the zinc hot-dip galvanizing layer of the intermediate article contained 8% by weight of Fe and 0.3% by weight of Mn.
  • the so-treated sample was subjected to examination for the presence (absence) of peeling and cracks as well as examination of the layer structure. The ⁇ and ⁇ 1 phases were observed, but the ⁇ phase was not observed. No cracking of the plating layer was observed in the zinc hot-dip galvanizing layer after the cooling.
  • a brown color was difficult to develop by treatment using the acidic solution containing an oxidizing agent, as in Example 1.
  • the brown oxide layer was easily removed by rubbing the plated layer.
  • a steel sheet (SS41) 50mm in width, 10mm in length, and 3.2mm in thickness was dipped for 30 minutes in an alkaline bath having a temperature of 80°C, to degrease it.
  • the steel sheet was then rinsed with hot water, and was then dipped for 30 minutes in a 10% hydrochloric acid solution at room temperature to descale it.
  • the steel sheet was subjected to a hot water-rise and then flux treatment using a 35% znCl2 - NH4Cl solution by dipping for 30 minutes in this solution at 60 °C.
  • the steel sheet which was subjected to the pretreatment as described above, was dipped for 1 minute in a plating bath containing 0.5% by weight of Mn, the balance being Zn at 480°C. After the zinc hot-dip galvanizing, the steel sheet was lifted above the plating bath and kept for 60 seconds in a furnace at 500°C so as to heat-treat the steel sheet. After the heat treatment, the steel sheet was allowed to cool, and then dipped for 1 minute in a sulfuric acid solution containing 4g/l of K2Cr2O7 and having pH of 2.
  • a uniform brown color corresponding to 5Y/Dk or the Hue and Tone graph was formed on the surface of the zinc hot-dip galvanizing layer.
  • the brown color developed was due to the oxide layer formed on the surface of the zinc hot-dip galvanizing layer.
  • the composition of the coating directly after the zinc hot-dip galvanizing was 0.5% by weight of Mn, 6% by weight of Fe, and the balance being Zn.
  • the ⁇ phase remained beneath the top layer, as contrary to that of Example 1. No cracks were therefore observed with an optical microscope at magnification of 200.
  • the production steps and period are shorter than those of a method, in which the zinc hot-dip galvanizing, undercoat treatment, and coating with brown paint are successively carried out.
  • brown oxide having good adherance is formed, and, further, even if such oxide peels, the underlying surface is oxidized to develop the brown color. The brown color is therefore maintained for a long period of time due to the color restoration.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Thermal Sciences (AREA)
  • Coating With Molten Metal (AREA)
EP90119534A 1989-04-27 1990-10-11 Color-coated article and method for producing the same Expired - Lifetime EP0423624B1 (en)

Applications Claiming Priority (8)

Application Number Priority Date Filing Date Title
JP1105819A JPH07110962B2 (ja) 1989-04-27 1989-04-27 着色亜鉛粉、その製造方法及び着色製品の製造方法
JP269047/89 1989-10-18
JP26904789 1989-10-18
JP125486/90 1990-05-17
JP2125486A JPH0765149B2 (ja) 1989-04-27 1990-05-17 着色メッキ方法及び被覆物
JP2131207A JP2612954B2 (ja) 1989-04-27 1990-05-23 茶色着色めっき被覆物
JP131207/90 1990-05-23
AU86007/91A AU645616B2 (en) 1989-04-27 1991-10-18 Color-coated article and method for producing the same

Publications (2)

Publication Number Publication Date
EP0423624A1 EP0423624A1 (en) 1991-04-24
EP0423624B1 true EP0423624B1 (en) 1996-01-24

Family

ID=27507279

Family Applications (1)

Application Number Title Priority Date Filing Date
EP90119534A Expired - Lifetime EP0423624B1 (en) 1989-04-27 1990-10-11 Color-coated article and method for producing the same

Country Status (4)

Country Link
EP (1) EP0423624B1 (ko)
KR (1) KR930009988B1 (ko)
AU (1) AU645616B2 (ko)
DE (1) DE69025022T2 (ko)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BR0313873B1 (pt) 2003-04-18 2013-05-28 chapas de aÇo galvanizadas por imersço a quente tendo excelente conformabilidade para prensagem e o mÉtodo para produÇço das mesmas.
KR100742833B1 (ko) * 2005-12-24 2007-07-25 주식회사 포스코 내식성이 우수한 고 망간 용융도금강판 및 그 제조방법
DE102006051384A1 (de) 2006-10-27 2008-04-30 Seppeler Holding Und Verwaltungs Gmbh & Co. Kg Verfahren zur Vorbewitterung von Metallteilen mit einer vorwiegend aus Zink bestehenden Oberfläche
JP5789208B2 (ja) * 2012-03-08 2015-10-07 株式会社神戸製鋼所 化成処理性と延性に優れた高強度合金化溶融亜鉛めっき鋼板とその製造方法
KR102349894B1 (ko) * 2015-01-29 2022-01-11 주식회사 만도 내장형 전자 제어 댐퍼

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB374826A (en) * 1929-12-31 1932-06-16 Ver Stahlwerke Ag Process for combating the formation of "white zinc rust" upon zinc and galvanised objects such as sheets, wires, tubes and the like
US3630792A (en) * 1969-04-28 1971-12-28 Cominco Ltd Process for the production of colored coatings
US4659631A (en) * 1984-05-17 1987-04-21 Sumitomo Metal Industries, Ltd. Corrosion resistant duplex plated sheet steel
EP0269006B1 (en) * 1986-11-21 1992-08-26 Nippon Mining Company Limited Colored zinc coating

Also Published As

Publication number Publication date
EP0423624A1 (en) 1991-04-24
AU645616B2 (en) 1994-01-20
KR910008159A (ko) 1991-05-30
KR930009988B1 (ko) 1993-10-13
DE69025022T2 (de) 1996-05-30
AU8600791A (en) 1993-05-13
DE69025022D1 (de) 1996-03-07

Similar Documents

Publication Publication Date Title
CN113316664A (zh) 合金涂覆钢板及其制造方法
DE2615515A1 (de) Metallueberzogene metallgegenstaende und verfahren zu deren herstellung
EP0423624B1 (en) Color-coated article and method for producing the same
SE508196C2 (sv) Förfarande för att bilda och eftertäta kromateringsskikt på elektrolytiskt utfälld zink
US6372296B2 (en) High aluminum galvanized steel
US5364478A (en) Method for producing a color-coated article
KR920004502B1 (ko) 착색아연 코우팅방법
JPH03229846A (ja) 溶融亜鉛メッキ方法
JP2794674B2 (ja) Ａｌ、Ａｌ合金またはこれらのめっき鋼板の黒色化処理方法
JPS6199664A (ja) 溶融亜鉛−アルミニウム合金めつき法
JPH05263208A (ja) 亜鉛系メッキ被覆物およびその製造方法
KR0125318B1 (ko) 건식 흑색 아연-구리 합금도금강판의 제조방법
JPH08302480A (ja) 塗装鋼板の製造方法
JPS63130756A (ja) 黄色の着色メツキの形成方法
JPH08188861A (ja) 合金化溶融亜鉛めっき鋼板の製造方法
JPH0617232A (ja) 耐食性に優れかつ外観の美麗なＳｉ／Ｚｎ２層メッキ鋼板およびその製造方法
JPS60194094A (ja) 高耐食性アルミニウム溶射鋼材
JPH01108396A (ja) カチオン電着塗装用ガルバニール鋼板の製法
JPH0765149B2 (ja) 着色メッキ方法及び被覆物
JPS6227536A (ja) 溶融亜鉛めつき用亜鉛合金及びその使用方法
EP0295980B1 (fr) Procédé pour la coloration de surfaces métalliques en zinc, zinguées et en alliage de ce métal
JPH08120483A (ja) 表面外観に優れた電気亜鉛めっき鋼板の製造方法
JPH04246193A (ja) 耐熱性および耐食性にすぐれた亜鉛めっき金属材料
KR920004503B1 (ko) 착색용융아연 코우팅용 아연합금 및 그것을 사용한 착색아연코우팅방법
JPS63241132A (ja) オリ−ブ灰色の着色メツキを形成する溶融メツキ用亜鉛合金及びその使用方法

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19901011

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): DE FR GB IT

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: NIPPON MINING & METALS COMPANY, LIMITED

17Q First examination report despatched

Effective date: 19940811

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): DE FR GB IT

ITF It: translation for a ep patent filed

Owner name: JACOBACCI & PERANI S.P.A.

REF Corresponds to:

Ref document number: 69025022

Country of ref document: DE

Date of ref document: 19960307

ET Fr: translation filed
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
REG Reference to a national code

Ref country code: GB

Ref legal event code: 732E

REG Reference to a national code

Ref country code: FR

Ref legal event code: CA

REG Reference to a national code

Ref country code: FR

Ref legal event code: TP

REG Reference to a national code

Ref country code: GB

Ref legal event code: 732E

REG Reference to a national code

Ref country code: FR

Ref legal event code: TP

Ref country code: FR

Ref legal event code: CA

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19981009

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19981016

Year of fee payment: 9

Ref country code: DE

Payment date: 19981016

Year of fee payment: 9

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19991011

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 19991011

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20000630

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20000801

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 20051011